CN101580345A - Method for preparing TCO film by ink jet printing - Google Patents
Method for preparing TCO film by ink jet printing Download PDFInfo
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- CN101580345A CN101580345A CNA2009100801437A CN200910080143A CN101580345A CN 101580345 A CN101580345 A CN 101580345A CN A2009100801437 A CNA2009100801437 A CN A2009100801437A CN 200910080143 A CN200910080143 A CN 200910080143A CN 101580345 A CN101580345 A CN 101580345A
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Abstract
The invention provides a method for preparing TCO film by ink jet printing, comprising the following steps: (1) using soluble compounds with metal bases of In, Sn and Zn and soluble compounds of doping elements as raw materials, dissolving in water or organic solvent; (2) adding additive for dispersing compound particles evenly and confecting into transparent conductive oxide ink with stable performance; (3) pouring the ink into an ink box and depositing on a substrate by ink jet printing technology; (4) performing thermal treatment to the film deposited on the substrate to form TCO film after reaction. The invention does not need vacuum environment, has simple device and process, and low preparation cost and short cycle, and can control the doping amount for preparing film randomly.
Description
Technical field
The present invention relates to the TCO thin film technique, specifically a kind of method of preparing TCO film by ink jet printing.
Background technology
TCO (transparent conductive oxide) is meant: visible light transmissivity is more than 80%, and resistivity is 10
-3The transparent conductive material that Ω cm is following.Usually obtain by in wide bandgap semiconductor, mixing impurity element.The TCO material mainly contains following three major types: In
2O
3Base film such as ITO, SnO
2Base film such as SnO
2: F, SnO
2: Sb etc., zno-based film such as ZnO:Al, ZnO:Ga etc.The TCO film, is widely used in solar cell, flat-panel monitor, gas sensor, antistatic coating, micro-wave screening and protective glasses and other photoelectric device near the electric conductivity of metal, the high-transmission rate in the visible-range, infrared high-reflectivity and characteristic of semiconductor with it.At many application, people attempt to obtain alap resistivity always, high as far as possible visible light transmissivity has correspondingly developed various method for manufacturing thin film such as evaporation technique, thermospray, chemical vapour deposition technique, sputter-deposition technology, sol-gel method.Wherein, magnetron sputtering, general chemical vapour deposition need be implemented under vacuum condition, and complicated operation, apparatus expensive, and preparation cost is higher.Thermospray and sol-gel method all are to use the soluble metal compound as presoma, generate oxygen containing metallic compound with water or organic solvent reaction, and thermal degradation gets transparent conductive oxide film, and characteristics are that technology is simple, the needing no vacuum environment.Based on these two kinds of technology, the present invention proposes a kind of more simple and easy to do film preparing technology---ink jet printing.
Ink jet printing is that the ink droplet that printhead produces is directly injected to the dielectric surface specific position through the aperture of nozzle under printing signal drives, and realizes the printing of character and figure.Inkjet technology is having outstanding advantage aspect the generation of fine droplet and the location.Ink-jet printer can be divided into piezo inkjet technology and hot ink-jet technology two major types by the mode of operation of printhead at present.Piezo inkjet technology is that many little piezoelectric ceramics are placed near the print-head nozzle of ink-jet printer, and the pressure wave that utilizes pulsed voltage to produce drives the ink droplet jetting nozzle.The ink jet-print head of making of piezo inkjet technology is strong to the controllability of ink droplet, realizes high-precision printing easily.Hot ink-jet technology is on the tube wall of shower nozzle well heater to be set, and under the electricimpulse effect, forms very little bubble on the well heater, and the bubble expanded by heating produces pressure-driven ink droplet jetting nozzle.The bubble printer so this ink-jet printer is otherwise known as sometimes.The general machine of printing disposes a plurality of ink-jet systems, and each ink-jet system connects with the print cartridge that the different colours ink is housed, and can print colourful pattern.Ink jet printing originally is one of major technique that generally adopts in the modern handle official bussiness printing, in recent years because its equipment is simple, easy and simple to handle, preparation cost is low etc. advantage, new application has also been arranged in the thin film technique field gradually, for example prepared membrane electrode of macromolecule membrane, film gas-sensitive material, lithium ion battery etc. with ink jet printing.The transparent conductive oxide film that utilizes this technology to prepare solar cell is expected to reduce the production cost of battery, and research yet there are no report about this respect.
Summary of the invention
It is low to the purpose of this invention is to provide a kind of preparation cost, simple to operate, the method for the preparing TCO film by ink jet printing of needing no vacuum environment.
To achieve these goals, technical scheme of the present invention is: operation as follows:
(1) is raw material with the soluble compound of metal_based materials such as In, Sn, Zn and the soluble compound of doped element, it is dissolved in water or the organic solvent together; Also can be dissolved in respectively in water or the organic solvent, mix two kinds of solution then.For making solution property stable, also can add the acidity of reagent regulator solutions such as hydrochloric acid;
(2) adding can make the homodisperse additive of compound particle, and add-on is 0.01~5% of water or an organic solvent weight, is 10~50mPas with the viscosity of controlling ink, and surface tension is 1.0 * 10
-4N/m~4.0 * 10
-4Between the N/m, be mixed with the metal oxide ink of stable performance;
(3) described ink is injected in the print cartridge, adopts conventional ink-jet printing technology to deposit on the substrate;
(4) the described film that deposits to substrate is placed constant temperature oven, at 100~600 ℃; Roasting, reaction forms the TCO film of certain doping ratio.
In addition, raw material is the nano particle of soluble compound described in the step of the present invention (1), as muriate, nitrate, acetate, metal alkoxide, ammonium salt etc.Muriate comprises InCl
35H
2O, SnCl
45H
2O, SnCl
22H
2O, SbCl
3, ZnCl
2, AlCl
3, GaCl
3Deng, nitrate has In (NO
3)
34.5H
2O, Al (NO
3)
3Deng, acetate has zinc acetate, ammonium acetate, Burow Solution etc., metal alkoxide that tin spirit, zinc alcohol, antimony alcohol, aluminum isopropylate, Virahol gallium etc. are arranged, and ammonium salt has NH
4F is dispersed in it in water or the organic solvent, and the weight ratio of described raw material and water or organic solvent is 1: 3~30.
At preparation SnO
2During base transparent conducting film, described doped element comprises one or more in the elements such as F, Sb, In, Zn, Al, Mn, Sr, Zr, Ge, Ce, Pt, Pd, Cd, Nd.
When preparation zno-based transparent conductive film, described doped element comprises one or more in the elements such as Al, Ga, In, B, N, P, As, Sb, F, Si, Ge, Sn, Y, Sc, Ti, Zr, Hf, Tb, Cd, Co, Rb, Li, Ni, Mn, Fe, Cr, Mg, Cu, Ce.
The mol ratio of the compound of described metallic compound sill and doped element is 1: 0.001~1.In preparation ITO electrically conducting transparent membrane process, the compound of described indium is (as InCl
3, In (NO
3)
3Deng) with the compound of tin (as SnCl
4, SnCl
2Deng) mol ratio be 1: 0.053~0.429, wherein, the doping ratio of tin is 5at%~30at%.
Water of the present invention is deionized water; Described organic solvent can be one or more in alcohols, methyl ethyl diketone, the ethylene glycol monomethyl ether etc., preferred dehydrated alcohol; Described additive is a tensio-active agent; Described tensio-active agent comprises anion surfactant, cats product, nonionic surface active agent or zwitterionics; Described anion surfactant is a stearate, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate etc.; Described cats product is a cetyl trimethylammonium bromide etc.; Described nonionic surface active agent is dodecyl diethanolamine, polyvinyl alcohol, glycerin fatty acid ester etc.Described zwitterionics is Yelkin TTS, amino acid, trimethyl-glycine etc.
The present invention has following advantage:
Employing the present invention can control the content of doped element in the TCO film easily, the needing no vacuum environment, and equipment is simple, and is easy and simple to handle, with low cost, also can prepare with In
2O
3, SnO
2, ZnO be the base polynary, multi-layer transparent conductive film.Unitary film can prepare respectively also and can prepare simultaneously in the multilayer film preparation.
Description of drawings
Fig. 1 is a piezoelectric ink jet printer plated film synoptic diagram
1---ink chamber, 2---battery lead plate, 3---piezoquartz, 4---the piezoquartz after the distortion, 5---nozzle plate, 6---ink droplet, 7---substrate
Fig. 2 is a thermal ink jet printers plated film synoptic diagram
1---ink chamber, 2---the pressure chamber, 3---well heater, 4---bubble, 5---nozzle plate, 6---ink droplet, 7---substrate
Wherein, Fig. 1 is a Figure of abstract.
Embodiment
Below only be preferred embodiment of the present invention, can not limit scope of the present invention with this.Promptly the equalization of being done according to the present patent application claim generally changes and modifies, and all should still belong in the scope that patent of the present invention contains.
Embodiment one
Preparation In
2O
3: the Sn film:
Operation as follows: 1) take by weighing 15g InCl
35H
2O and 1.88gSnCl
45H
2O is a raw material, and it is dissolved in the 100ml deionized water; 2) adding tensio-active agent dodecyl diethanolamine 3.5g, is that 35mPas, surface tension are 3.5 * 10 with the viscosity of controlling ink
-4N/m; 3) described ink is injected in the print cartridge, adopts conventional piezoelectric ink jet printing technology to spray on the glass substrate of heat; 4) glass substrate is heated to 460 ℃ in constant temperature oven, the doping that reaction forms tin is the In of 10at%
2O
3: the Sn film.
Embodiment two
Preparation In
2O
3: the Sn film:
Operation as follows: 1) take by weighing 10g InCl
35H
2O and 1.28gSnCl
22H
2O is a raw material, and it is dissolved in the 100ml deionized water; 2) adding tensio-active agent cetyl trimethylammonium bromide 1.5g, is that 25mPas, surface tension are 2.5 * 10 with the viscosity of controlling ink
-4N/m; 3) described ink is injected in the print cartridge, adopts the piezoelectric ink jet printing technology to spray on the glass substrate of heat; 4) glass substrate is placed constant temperature oven, be heated to 500 ℃, the doping that reaction forms tin is the In of 15at%
2O
3: the Sn film.
Embodiment three
Preparation In
2O
3: the Sn film:
Operation as follows: 1) take by weighing 20gIn (NO
3)
34.5H
2O and 7.87gSnCl
45H
2O is a raw material, with In (NO
3)
34.5H
2O is dissolved in the 100ml methyl ethyl diketone, with SnCl
45H
2O is dissolved in the 100ml ethylene glycol monomethyl ether; 2) with above-mentioned two kinds of solution mixing and stirring; 3) adding tensio-active agent sodium lauryl sulphate 2.0g, is that 20mPas, surface tension are 2.0 * 10 with the viscosity of controlling ink
-4N/m; 4) described ink is injected in the print cartridge, adopts hot ink-jet printing technology to spray on the glass substrate of heat; 5) glass substrate is placed constant temperature oven, be heated to 550 ℃, the doping that reaction forms tin is the In of 30at%
2O
3: the Sn film.
Embodiment four
Preparation In
2O
3: the Sn film:
Operation as follows: 1) take by weighing 20g InCl
35H
2O and 7.51gSnCl
45H
2O is a raw material, and it is dissolved in the 100ml deionized water; 2) adding tensio-active agent Yelkin TTS 1.0g, is that 10mPas, surface tension are 1.0 * 10 with the viscosity of controlling ink
-4N/m; 3) described ink is injected in the print cartridge, adopts conventional hot ink-jet printing technology to spray on the glass substrate of heat; 4) glass substrate is placed constant temperature oven, be heated to 550 ℃, the doping that reaction forms tin is the In of 25at%
2O
3: the Sn film.
Embodiment five
Preparation SnO
2: the F film, operation steps is as follows:
1) gets 10g SnCl
45H
2O and 0.35gNH
4F is a raw material, it is dissolved in the 37.5ml deionized water, and adds the 2.5ml concentrated hydrochloric acid, and violent stirring is configured to stable transparent acid solution; 2) adding tensio-active agent cetyl trimethylammonium bromide 0.8g, is that 20mPas, surface tension are 2.0 * 10 with the viscosity of controlling ink
-4N/m; 3) described ink is injected in the print cartridge, adopts the piezoelectric ink jet printing technology to spray on the glass substrate; 4) deposit to on-chip film be heated to 150 ℃ in constant temperature oven described, it is the SnO of 25at% that reaction forms doping
2: the F film.
Embodiment six
Preparation SnO
2: the Sb film, operation steps is as follows:
1) gets 10g SnCl
22H
2O is dissolved in the 50ml dehydrated alcohol, 80 ℃ stirred in water bath 3 hours, it is fully dissolved then, generates HCl and tin spirit in dissolution process; 2) get 0.21g SbCl
3Be dissolved in the 50ml dehydrated alcohol, also 80 ℃ stirred in water bath 4 hours, this reaction generated HCl and antimony alcohol; 3) above-mentioned two kinds of solution thorough mixing were stirred 4 hours, left standstill again 24 hours; 4) adding tensio-active agent sodium stearate 0.3g in above-mentioned mixing solutions, is that 15mPas, surface tension are 1.5 * 10 with the viscosity of controlling ink
-4N/m; 5) described ink is injected in the print cartridge, adopts conventional piezoelectric ink jet printing technology to spray on the glass substrate; 6) deposit to on-chip film be heated to 400 ℃ in constant temperature oven described, tin spirit and antimony alcohol resolve into deserved oxide compound, and forming doping is the SnO of 2at%
2: the Sb film.
Embodiment seven
Preparation ZnO:Al film:
Operation as follows: 1) get 20g Zn (CH
3COO)
22H
2O and 1.11gAl (NO
3)
39H
2O is a raw material, and it is dissolved in the 200ml deionized water; 2) add tensio-active agent sodium lauryl sulphate 0.3g, add-on is 0.15% of a water weight, is that 15mPas, surface tension are 1.5 * 10 with the viscosity of controlling ink
-4N/m; 3) described ink is injected in the print cartridge, adopts conventional piezoelectric ink jet printing technology to spray on the glass substrate; 4) deposit to on-chip rete be heated to 370 ℃ in constant temperature oven described, it is the ZnO:Al film of 3.14at% that reaction forms doping.
Embodiment eight
Preparation ZnO:Ga film:
Operation as follows: 1) get 10g ZnCl
2Be raw material, be dissolved in the 50ml dehydrated alcohol, 60 ℃ stirred in water bath 2 hours, it is fully dissolved then, in dissolution process, generate HCl and zinc alkylol cpd; 2) get 0.3g GaCl
3Be dissolved in the 50ml dehydrated alcohol, also, generate HCl and gallium alkylol cpd in this process 60 ℃ stirred in water bath 2 hours; 3) above-mentioned two kinds of solution thorough mixing were stirred 4 hours, left standstill again 24 hours; 4) adding tensio-active agent cetyl trimethylammonium bromide 0.3g in above-mentioned mixing solutions, is that 15mPas, surface tension are 1.5 * 10 with the viscosity of controlling ink
-4N/m; 5) described ink is injected in the print cartridge, adopts conventional piezoelectric ink jet printing technology to spray on the glass substrate; 6) deposit to on-chip rete be heated to 350 ℃ in constant temperature oven described, forming doping is the ZnO:Ga film of 2.27at%.
Embodiment nine
Preparation ZnO:N film:
Operation as follows: 1) get 10g Zn (CH
3COO)
22H
2O zinc and 0.4g ammonium acetate CH
3COONH
4Be raw material, it is dissolved in the 100ml deionized water; 2) add tensio-active agent dodecyl diethanolamine 0.2g, add-on is 0.2% of a water weight, is that 20mPas, surface tension are 2.0 * 10 with the viscosity of controlling ink
-4N/m; 3) described ink is injected in the print cartridge, adopts conventional hot ink-jet printing technology to spray on the glass substrate; 4) deposit to on-chip rete be heated to 370 ℃ in constant temperature oven described, it is the ZnO:N film of 10at% that reaction forms doping.
Embodiment ten
Preparation SnO
2: (Sb, Zn) film, operation steps is as follows:
1) gets 10g SnCl
22H
2O is dissolved in the 100ml dehydrated alcohol, 80 ℃ stirred in water bath 3 hours, it is fully dissolved then, generates HCl and tin spirit compound in dissolution process; 2) get 0.32g SbCl
3Be dissolved in the 50ml dehydrated alcohol, also 80 ℃ stirred in water bath 4 hours, this reaction generated HCl and antimony alkylol cpd; Get 0.19g ZnCl
2Be dissolved in the 50ml dehydrated alcohol, 80 ℃ stirred in water bath 2 hours, this reaction generated HCl and zinc alkylol cpd 3) will above-mentioned two kinds of solution thorough mixing stirring 4 hours, left standstill again 24 hours; 4) adding tensio-active agent glycerin fatty acid ester 0.2g in above-mentioned mixing solutions, is that 10mPas, surface tension are 1.0 * 10 with the viscosity of controlling ink
-4N/m; 5) described ink is injected in the print cartridge, adopts conventional hot ink-jet printing technology to spray on the glass substrate; 6) deposit to on-chip film be heated to 375 ℃ in constant temperature oven described, the formation doping is the SnO of 3at%Sb, 3at%Zn
2Base film.
Embodiment 11
Preparation SnO
2: the F/ZnO:Al bilayer film, operation steps is as follows:
1) gets 10g SnCl
45H
2O and 0.3gNH
4F is a raw material, it is dissolved in the 37.5ml deionized water, and adds the 2.5ml concentrated hydrochloric acid, and violent stirring is configured to stable transparent acid solution; 2) adding tensio-active agent Yelkin TTS 0.4g, is that 20mPas, surface tension are 2.0 * 10 with the viscosity of controlling ink
-4N/m; 3) described ink is injected in the print cartridge, adopts conventional hot ink-jet printing technology to spray on the glass substrate; 4) deposit to on-chip rete be heated to 150 ℃ in constant temperature oven described, reaction forms SnO
2: the F film; 5) get 20g Zn (CH
3COO)
22H
2O and 1.11gAl (NO
3)
39H
2O is a raw material, and it is dissolved in the 200ml deionized water; 6) add tensio-active agent Yelkin TTS 0.4g, add-on is 0.2% of a water weight, is that 20mPas, surface tension are 2.0 * 10 with the viscosity of controlling ink
-4N/m; 7) described ink is injected in the print cartridge, adopts conventional hot ink-jet printing technology to spray on the glass substrate; 8) deposit to on-chip rete be heated to 400 ℃ in constant temperature oven described, reaction forms the ZnO:Al film.
Embodiment 12
The ZnO film of Al and Ga is mixed in preparation:
Operation as follows: 1) get 20gZnCl
2, it is dissolved in the 100ml dehydrated alcohol, insert return channel, the control reflux temperature is 60 ℃, and return time is 2 hours, and reaction generates HCl and zinc alkylol cpd in this process; 2) get 0.95g aluminum isopropylate Al (OC
3H
7)
3With 0.76g Virahol gallium Ga (OC
3H
7)
3Be dissolved in respectively in the 50ml dehydrated alcohol; 3) above-mentioned three kinds of solution are mixed, stir, add tensio-active agent trimethyl-glycine 0.3g, add-on is 0.15% of an organic solvent weight, is that 15mPas, surface tension are 1.5 * 10 with the viscosity of controlling ink
-4N/m; 3) described ink is injected in the print cartridge, adopts conventional hot ink-jet printing technology to spray on the glass substrate; 4) deposit to on-chip rete be heated to 350 ℃ in constant temperature oven described, it is the zno-based film of Al3at%, Ga2at% that reaction forms doping.
Claims (11)
1. the method for a preparing TCO film by ink jet printing is characterized in that operating as follows:
(1) is raw material with the soluble compound of In, Sn, Zn metal_based material and the soluble compound of doped element, it is dissolved in water or the organic solvent;
(2) adding can make the homodisperse additive of compound particle, is mixed with the transparent conductive oxide ink of stable performance;
(3) ink is injected in the print cartridge, adopts ink-jet printing technology to deposit on the substrate;
(4) film that will deposit to substrate is through thermal treatment, and reaction forms the TCO film.
2. method according to claim 1 is characterized in that, raw material is the nano particle of muriate, nitrate, acetate, metal alkoxide or ammonium salt, and it is dispersed in water or the organic solvent.
3. method according to claim 2 is characterized in that, raw material is InCl
35H
2O, SnCl
45H
2O, SnCl
22H
2O, SbCl
3, ZnCl
2, AlCl
3, GaCl
3In (NO
3)
34.5H
2O, Al (NO
3)
3Zinc acetate, ammonium acetate, Burow Solution; Tin spirit, zinc alcohol, antimony alcohol, aluminum isopropylate, Virahol gallium; Or NH
4F.
4. method according to claim 1 is characterized in that, the doped element of In base film is Sn; The doped element of Sn base film is one or more among F, Sb, In, Zn, Al, Mn, Sr, Zr, Ge, Ce, Pt, Pd, Cd or the Nd; The doped element of Zn base film is one or more among Al, Ga, In, B, N, P, As, Sb, F, Si, Ge, Sn, Y, Sc, Ti, Zr, Hf, Tb, Cd, Co, Rb, Li, Ni, Mn, Fe, Cr, Mg, Cu or the Ce.
5. method according to claim 1 is characterized in that, water is deionized water, and organic solvent is one or more in alcohols, methyl ethyl diketone or the ethylene glycol monomethyl ether.
6. according to described any one method of claim 1~5, it is characterized in that the mol ratio of the compound of metal_based material and the compound of doped element is 1: 0.001~1.
7. according to described any one method of claim 1~6, it is characterized in that the weight ratio of raw material and water or organic solvent is 1: 3~30.
8. according to described any one method of claim 1~7, it is characterized in that the additive add-on is 0.01~5% of water or an organic solvent weight, the viscosity of ink is 10~50mPas, and surface tension is 1.0 * 10
-4N/m~4.0 * 10
-4N/m.
9. according to claim 1,8 described methods, it is characterized in that additive is anion surfactant, cats product, nonionic surface active agent or zwitterionics.
10. method according to claim 9 is characterized in that tensio-active agent is selected from: stearate, Sodium dodecylbenzene sulfonate or sodium lauryl sulphate; Cetyl trimethylammonium bromide; Dodecyl diethanolamine, polyvinyl alcohol or glycerin fatty acid ester; Yelkin TTS, amino acid or trimethyl-glycine.
11. according to described any one method of claim 1~10, it is characterized in that, adopt present method prepare different doped elements with In
2O
3, SnO
2, ZnO be the base multielement or multi-layer transparent conductive film.
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101805132A (en) * | 2010-03-26 | 2010-08-18 | 洛阳新晶润工程玻璃有限公司 | Method for improving high temperature resistance of temperable low-radiation coated glass |
WO2012041853A3 (en) * | 2010-09-27 | 2012-05-31 | The Technical University Of Denmark | Improved adhesion of metal oxide layer |
CN102775847A (en) * | 2012-07-16 | 2012-11-14 | 中国科学院宁波材料技术与工程研究所 | Ink used for preparing zinc oxide-based film and preparation method thereof |
CN104108248A (en) * | 2013-04-19 | 2014-10-22 | 中国科学院理化技术研究所 | Liquid metal ink-jet printing equipment and printing method |
WO2017186094A1 (en) * | 2016-04-29 | 2017-11-02 | 京东方科技集团股份有限公司 | Thin-film transistor and manufacturing method, array substrate and manufacturing method, display panel, and display device |
-
2009
- 2009-03-24 CN CNA2009100801437A patent/CN101580345A/en active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101805132A (en) * | 2010-03-26 | 2010-08-18 | 洛阳新晶润工程玻璃有限公司 | Method for improving high temperature resistance of temperable low-radiation coated glass |
CN101805132B (en) * | 2010-03-26 | 2012-11-28 | 洛阳新晶润工程玻璃有限公司 | Method for improving high temperature resistance of temperable low-radiation coated glass |
WO2012041853A3 (en) * | 2010-09-27 | 2012-05-31 | The Technical University Of Denmark | Improved adhesion of metal oxide layer |
CN102775847A (en) * | 2012-07-16 | 2012-11-14 | 中国科学院宁波材料技术与工程研究所 | Ink used for preparing zinc oxide-based film and preparation method thereof |
CN102775847B (en) * | 2012-07-16 | 2014-10-08 | 中国科学院宁波材料技术与工程研究所 | Ink used for preparing zinc oxide-based film and preparation method thereof |
CN104108248A (en) * | 2013-04-19 | 2014-10-22 | 中国科学院理化技术研究所 | Liquid metal ink-jet printing equipment and printing method |
WO2017186094A1 (en) * | 2016-04-29 | 2017-11-02 | 京东方科技集团股份有限公司 | Thin-film transistor and manufacturing method, array substrate and manufacturing method, display panel, and display device |
US10497563B2 (en) | 2016-04-29 | 2019-12-03 | Boe Technology Group Co., Ltd. | Thin film transistor and method for manufacturing the same, array substrate and method for manufacturing the same, display panel and display device |
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